Dioxazine dyestuffs having in 6 and 13 position a heterocyclic acylamino group



United States Patent 3,480,625 DIOXAZlNE DYESTUFFS HAVING IN 6 AND 13 POSITION A HETEROCYCLIC ACYLAMINO GROUP Karl Ronco, Riehen, and Istvan Hari, Basel, Switzerland,

assignors to Ciba Limited, Basel, Switzerland, a company of Switzerland N0 Drawing. Filed Jan. 17, 1967, Ser. No. 609,744 Claims priority, applicatigo: /S6vgitzerland, Jan. 25, 1966,

Int. Cl. C09b 19/02; C07d 87/48 US. Cl. 260-446 6 Claims ABSTRACT OF THE DISCLOSURE The present invention concerns pigment dystulfs of the triphendioxazine series. They are characterized by the presence in each of the 6 and 13 positions of an acylamino group which is derived from a heterocyclic carboxylic acid, especially a pyridine or thiophene carboxylic acid.

. Use.For coloring high molecular organic products,

I such as plastics and lacquers.

The present invention is based on the observation that new, valuable dioxazine dyestuffs of the formula (1) NHC CR1 NBC OR:

in which A represents an ortho-arylene residue, R represent a heterocyclic residue and R represents a heterocyclic residue or an aryl residue, can be obtained when a 3,6- bis-(aroylamino)-1,4-benzoquinone of the formula IIHCORi O- NHA! ArHN -O I IHCORr in which R, and R have the meanings given above and A represents an, aryl residue preferably containing an ether group in ortho-position to the NH- group, is subjected to ring-closure with the formation of a dioxazlne.

The 3,6-bis-(aroylamino)-1,4-benzoquinones used as starting materials preferably correspond to the formula NHCOR X OR O NH NH 0 R0 Y NHOORi in which R represents a heterocyclic residue, R represents an alkyl or an aryl residue, X represents a hydrogen or a halogen atom or an alkyl, alkoxy, aralkoxy, aryloxy, carbalkoxy, carbophenoxy, nitro, cyano, acylamino, trifluoromethyl, alkylsulphonyl, arylsulphonyl, aryl, alkylmercapto or arylmercapto group and Y represents a hydrogen or a halogen atom or an alkyl, alkoxy or nitro group.

The 3,6-bis-(aroylamino)-1,4-benzoquinones may ad- 3,480,625 Patented Nov. 25, 1969 "ice vantageously be prepared by condensing one mol of a parabenzoquinone of the formula with two mols of an arylamine containing an ether group in ortho-position to the amino group, especially an orthoalkoxyor an ortho-phenoxyaminobenzene. The following arylamines may be mentioned as examples:

1-amino-2-rnethoxybenzene, 1-amino-2,3-diethoxybenzene, 1-an1ino-2,4-dimethoxybenzene, 1-amino-2,4-diethoxybenzene, 1-amino-2,4-diphenoxybenzene, 1-an1ino-2,S-diphenoxybenzene, 1-amino-2,4-diethoxy-5-chlorobenzene, 1-amino-2,4-diphenoxy-5-cl1l0robenzene, 1-amino-2,S-dirnethoxybenzene, 1-amino-2,5-diethoxybenzene, 1-amino-2-Inethoxy-3 -methylbenzene, 1-amino-2-methoxy-4-methylbenzene, 1-amino-2-rnethoxy-S-methylbenzene, 1amino-Z-methoxy-B-chlorobenzene, 1-amin0-2- methoxy-4-chlorobenzene, 1-amino-2-methoxy-5-chlorobenzene, 1-amino-2-methoxy-4-nitrobenzene, 1-amino-2-methoxy-5-benzoylbenzene, 1-amino-2-methoxy-5-acety1benzene, 1-amino-2-methoxy-4-cyanobenzene, 1-amino-2-methoxy-5-methylsulphonylbenzene, 1-arnino-2- rnethoxy-5 -phenylsulphonylbenzene, 1-amino-Z-methoxy-S-phenylbenzene, 1-aunino-2-methoxy-5-trifluoromethylbenzene, l-amino-Z-rnethoxy-S-carb alkoxybenzene, 1-amino-Z-methoxy-S-carbophenoxybenzene, 1-amino-2-methoxy-4-acetylarninobenzene, 1-arnino-2-methoxy-4-benzoylaminobenzene,

1- mino-Z,5-dimethoxy-4-acetylaminobenzene, 1amino-2,5-dimethoxy-4-benzoylarninobenzene, 1-amino-2,S-diethoxy-4-benzoylaminobenzene, 1-amino-2-methoxy-4-benzoylamino-5-methylbenzene, 1-amino-2-rnethoxy-4-benzoylamino-S-chlorobenzene, 1-amino2-methoxy-5-benzoylaminobenzene, 1-amino-2- methoxy-naphthalene and Z-amino-l-methoxynaphthalene.

The heterocyclic residue R in the compounds of the Formulae 1 to 3 is preferably a monocyclic heterocyclic residue. The following carboxylic acids containing a heterocyclic residue R may be mentioned as examples: furan-Z-carboxylic acid, thiophene-2-carboxylic acid, 2-carbomethoxythiophene-S-carboxylic acid, Z-phenylthiophene-5-carboxylic acid, pyridine-Z-carboxylic acid, pyridine-3-carboxylic acid, pyridine-4-carboxylic acid, quinoline-Z-carboxylic acid, 2-phenylquinoline-4-carboxylic acid, 2-phenylthiazo1e-4-carboxy1ic acid and l-phenyl-1,2,3-triazole-4-carboxy1ic acid,

Dioxazine ring-closure is advantageously performed at a temperature within the range of from to 200 C. in an inert organic solvent, for example, ortho-dichlorobenzene, trichlorobenzene, nitrobenzene, naphthalene or chloronaphthalene, if desired or required, in the presence of an acid chloride, for example, benzoyl chloride, paratoluenesulphonic acid chloride or thionyl chloride.

To simplify the synthesis, the reaction between the dichlorodiacylamino-1,4-benzoquinone of the Formula 3 and the arylamine and the subsequent ring-closure to form the dioxazine can be carried out in the same vessel without isolation of the intermediate product.

The products obtained are valuable red to blue dyestuffs which are primarily suitable for use as pigments and have a very broad field of application. For example, they can be used in a state of fine division for the spin colouration of filament and staple-fibre viscose, cellulose ethers, cellulose esters, polyamides, polyurethanes and polyesters, in the preparation of coloured lacquers and lake formers, coloured solutions and products made from cellulose acetate, nitrocellulose, natural resins and synthetic resins, for example, polymerization resins or condensation resins, for example, aminoplasts, alkyd resins, phenoplasts, polyolefines, for example, polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrlyonitrile, rubber, casein, and silicones and silicone resins. They are also suitable for use in the manufacture of coloured pencils, cosmetic preparations and laminated sheet material.

The following examples illustrate the invention. Unless otherwise stated, the parts and percentages are by weight.

EXAMPLE 1 10.3 parts of 2,5-dibromo-3,6-bis-(2-thiophenoylarnino)1,4-benzoquinone and 7.4 parts of 2,4-diethoxyaniline are heated to 200 C. within 60 minutes in the presence of 6.6 parts of anhydrous sodium acetate in 120 parts of a-chloronaphthalene while stirring. After formation of the dianil, ring-closure to form the dioxazine is carried out directly at 200 to 210 C. for 30 minutes. The uniformly crystalline red pigment which forms is isolated by filtration at 120 C., washed with hot a-chloronaphthalene, methanol, water and methanol, and then dired in vacuo at 60 to 70 C. When used in a state of fine division, it colours PVC film scarlet tints having a very good fastness to migration and to light.

NH HGCH The pigment corresponds to the formula H(If fiH (|30O\ /CH 11111 S O N H5030 Ny O 02115 10.3 parts of 2,5-dibromo-3,6-bis-(2-thiophen0ylamino)-1,4-benzoquinone and 13 parts of 2,5-diethoxy-4- benzoylaminoaniline are heated to 200 C. within 60 minutes in the presence of 6.6 parts of anhydrous sodium acetate in 150 parts of a-chloronaphthalene while stirring. After formation of the dianil, ring-closure to form the dioxazine is carried out directly at 200 to 210 C. for

4 minutes. The crystalline, blue pigment which forms is isolated by filtration at C., washed with hot oc-ChlOlO- naphthalene, methanol, water and methanol and then dreid in vacuo at 60 to 70 C.

The product of the formula is a reddish blue pigment which is sparingly soluble to insoluble in the common solvents and colours polyvinyl chloride film reddish blue tints possessing a very good fastness to light, to migration and to over-lacquering.

Pigments having colours ranging through red and violet to blue and similar properties of fastness are obtained when the 2,5-diethoxy-4-benzoylaminoaniline is replaced by an equivalent proportion of 2,5-dimethoxy-4-benzoylaminoaniline, Z-methoxy-5-methyl-4-benzoylaminoaniline, 2-meth0xy-5-chl0ro4-benzoylaminoaniline, 2,5-diethoxy- 4 (4'-chloro)-benzoylaminoaniline, 2,5-diethoxy-4-(4'- methoxy)-benzoylaminoaniline, 2,5 diethoxy-4-(4'-carbomethoxy) benzoylaminoaniline, 2,5-diethoxy-4-acetylaminoaniline or 2,5-dimethoxy-4-formylaminoaniline, or when the 2,5-dibromo-3,6-bis-(2-thiophenoylamino)-1,4- benzoquinone is replaced by an equivalent amount of 2,5 dibromo 3,6-bis-(Z-furanoylamino)-l,4-benzoquinone.

EXAMPLE 3 EXAMPLE 4 10.9 parts of 2,5-dichloro-3,6-bis-(5-carbomethoxy-2- thiophenoylamino)-1,4-benzoquinone and 7.4 parts of 2,4-diethoxyaniline are heated in the manner described in Example 1 in the presence of 6.6, parts of anhydrous sodium acetate in 120 parts of a-chloronaphthalene. The reaction product is worked up in the manner described in Example 1. The new pigment corresponds to the formula When used in a state of fine division, it colours polyvinyl chloride scarlet tints possessing a good fastness to migration and to light.

A pigment having a similar tint and similar properties of fastness is obtained by replacing the 2,4-diethoxyaniline with an equivalent amount of 2,5-diethoxyaniline.

EXAMPLE 5 g g 9.7 parts of 2,5-dichloro-3,6-bis-(2,4-dimethyl-5=thiazolylamino)-1,4-benzoquinone and 7.4 parts of 2,4-diethoxyaniline are heated in the manner described in Example 1 in the presence of 6.6 parts of anhydrous sodium acetate in 120 parts of a-chloronaphthalene. The pigment of the formula H aCfi OCH N/ o 3 6 C-CH:

tints.

EXAMPLE 6 20 parts of 2,5-dinicotinoylamino-3,6-di-(2',5'-diethoxy- 4' benzoylaminophenylamino) 1,4 benzoquinone, prepared by condensing 2,5-dinicotinoylamino-3,6-dichloro- 1,4 benzoquinone and 1 amino 4 benzoylamino 2,5 diethoxybenzene in isopropanol in the presence of sodium acetate, are slowly heated to the boil in 150 parts of orthodichlorobenzene, the alcohol split ofi during closure of the dioxazine ring being removed by distillation. The batch is kept at a gentle boil for 4 hours while stirring, cooled to 120 C., and filtered. Working up is effected in the manner described in Example 2. The pigment so obtained corresponds to the formula and colours polyvinyl chloride film fast blue tints.

A pigment having similar colouration properties is obtained by using 2,5-dipicolinoylor diisonicotinoylamino- 3,6 bis (2,5' diethoxy 4' benzoylaminophenylamino)-1,4-benzoquinone as starting material.

EXAMPLE 7 9.1 parts of 2,5 dichloro 3 (ot-thiophenoylamino)- 6 (2' chlorobenzoylamino) 1,4-benz0quinone and 7.4 parts of 2,4-diethoxyaniline are heated in the manner described in Example 1 in the presence of 6.6 parts of anhydrous sodium acetate in 120 parts of ct-chloronaphthalene. The new pigment so obtained corresponds to the formula It colours polyvinyl chloride scarlet tints having a very good fastness to migration and to light.

Pigments having a similar tint and similar properties of fastness are obtained when the 2,5-dichloro 3-(2-thiophenoylamino) 6 (2' chlorobenzoylamino) 1,4- benzoquinone is replaced by an equivalent amount of 2,5 dichloro 3 (2 thiophenylamino) 6 benzoylamino 1,4 benzoquinone, 2,5 dichloro 3 (Z-furanoylamino)-6-benzoylamino-1,4-'benzoquinone, 2,5-dichloro- 3 (2 furanoylamino) 6 (2 chlorobenzoylamino)- 1,4 benzoquinone or 2,5 dichloro 3 (2 thiophenoylamino) 6 (2',4 dichlorobenzoylamino) 1,4 benzoin which R represents a heterocyclic radical selected from the group consisting of pyridine, furane, thiophene, picolinyl, 5-carbomethoxy-Z-thiophenyl and 2,4-dimethyl-5- thiazolyl, X represents a hydrogen, a halogen lower alkyl, lower alkoxy, phenoxy, nitro, cyano or benzoylamino, 4 methoxybenzoylamino, 4'-carbomethoxybenzoylamino and 4'-chlorobenzoylamino and Y represents a hydrogen, a halogen or lower alkyl or lower alkoxy or nitro.

\ 0 our.

HsCaO o \N/ claim 1 of the formula \S IITH O N OONH OCzHI NHOOO ITTH 00 s U 4. The dyes tuff as claimed in claim 1 of the formula 6. The dyeetuff as claimediin claim 1 of the formula O-CONH (I: 0 T o moon HzdzO- NHCO O 1 r O 0 References Cited UNITED STATES PATENTS 5. The dyestufi as elaimediu claim 1 of the formula 3,065,229 11/1962 Ronco 260 246 j 20 FOREIGN PATENTS l 1,374,546 8/1964 France. 1 S OTHER REFERENCES 7 Q I N Ciba Chem. Abst., vol. 59, column 5294 (1963). 0 02115 25 a I HENRY R. JILES, Primary Examiner NUO NATALIE T ousoF, Assistant Examiner ll m 30 Us. 01. X.R. Coil 260-37, 38, 39, 40, 41', 41.5, 295, 295.5, 308, 332.2,

CASE 5855/E @3233? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 30,625 Dated November 25, 1169 Inven fl KARL RONCO ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 6, lines 63 to 7H, amend the middle of the formula to read:

war-.9 mu $511.20 JAN 5 1971 a t: mm: 2. SGEUYIIB, JR.

Gomlasioner of Patents Edward M. Fletcher, 1f,

Attcsting Officer 

